Open AccessStrongly Luminescent Pt(IV) Complexes with a Mesoionic N-Heterocyclic Carbene Ligand: Tuning Their Photophysical Properties
Author(s) -
Ángela Vivancos,
Adrián Jiménez-García,
Delia Bautista,
Pablo GonzálezHerrero
Publication year - 2021
Publication title -
inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 233
eISSN - 1520-510X
pISSN - 0020-1669
DOI - 10.1021/acs.inorgchem.1c00410
Subject(s) - mesoionic , chemistry , carbene , ligand (biochemistry) , phosphorescence , luminescence , aryl , electrochemistry , photochemistry , homo/lumo , medicinal chemistry , stereochemistry , molecule , fluorescence , organic chemistry , catalysis , electrode , biochemistry , physics , receptor , alkyl , optoelectronics , quantum mechanics
The synthesis, electrochemistry, and photophysical properties of a series of bis-cyclometalated Pt(IV) complexes that combine the mesoionic aryl-NHC ligand 4-butyl-3-methyl-1-phenyl-1 H -1,2,3-triazol-5-ylidene (trz) with either 1-phenylpyrazole or 2-arylpyridine (C ∧ N) are reported. The complexes ( O C -6-54)-[PtCl 2 (C ∧ N)(trz)] bearing cyclometalating 2-arylpyridines present phosphorescent emissions in the blue to yellow color range, which essentially arise from 3 LC(C ∧ N) states, and reach quantum yields of ca. 0.3 in fluid solutions and almost unity in poly(methyl methacrylate) (PMMA) matrices at 298 K, thus representing a class of strong emitters with tunable properties. A systematic comparison with the homologous C 2 -symmetrical species ( OC -6-33)-[PtCl 2 (C ∧ N) 2 ], which contains two equal 2-arylpyridine ligands, shows that the introduction of a trz ligand leads to significantly lower nonradiative decay rates and higher quantum efficiencies. Computational calculations substantiate the effect of the carbene ligand, which raises the energy of dσ* orbitals in these derivatives and results in the higher energies of nonemissive deactivating 3 LMCT states. In contrast, the isomers ( OC -6-42)-[PtCl 2 (C ∧ N)(trz)] are not luminescent because they present a 3 LMCT state as the lowest triplet.